Bioengineering functional copolymers. VIII. stimuli-responsive boron-containing graft copolymers and their poly(ethylene imine) macrocomplexes and DNA conjugates

Bioengineering functional copolymers. VIII. stimuli-responsive boron-containing graft copolymers and their poly(ethylene imine) macrocomplexes and DNA conjugates

New boron-containing graft copolymers and their poly(ethylene imine) (PEI) macrocomplexes were synthesized by amidolysis of poly(N-isopropylacrylamide-co-maleic anhydride)s [poly(NIPA-co-MA)s] with ethanolamine ester of diphenylboronic acid (EAPB), and following complexation of graft copolymers with poly(ethylene imine) (PEI), respectively. The structure, compositions and properties (stimuli-responsive, polyelectrolyte and thermal behavior) of synthesized copolymers were characterized by FTIR, 1H {13C} NMR and UV spectroscopy, viscometry, DSC and TGA analyses. It was shown that under given conditions (pH, temperature and grafting degree), these H-bonding macrocomplexes with hydrophobic diphenylborate side chain groups in aqueous solutions undergo a reversible cooperative conformational transition which is provided a promising possibility of adjusting the hydophobic–hydrophilic balance in the studied graft copolymer systems. Fluorescence measurements indicated that poly[(NIPA-co-MA)-g- EAPB]/PEI macrocomplex easily transferred to the HELA tumor cells, and showed low cytotoxicity against a normal cell line. Obtained results, especially stimuli-responsive and very high transferable behavior allow use these boroncontaining graft copolymer systems as non-viral vectors in gene- and bioengineering processes and drug delivery systems, as well as in boron neutron capture therapy.

___

  • 1. Shull BK, Spielvogel DE, Gopalaswamy R, Sankar S, Boyle PD, Head G and Detivo, K, J Chem Soc Perkin Trans 2:557 (2000).
  • 2. Hall IH, Henry JR, Peaty, NJ, Barnes BJ and Pawelke G, Appl Organomet Chem 14:86 (2000).
  • 3. Carter CAG, Vogels CM, Harrison DJ, Gagnon MKJ, Norman DW, Langler RF, Baker RT and Westcott SA, Organometallics 20:2130 (2001).
  • 4. Stoll VS, Eger DT, Hynes RC, Martichonok V, Jones JB and Pai, EF, Biochemistry 37:451 (1998).
  • 5. Westmark PR, Gardiner SJ and Smith BD, J Am Chem Soc 118:11093 (1996).
  • 6. Busse PM, Zamenhof RG, Harling OK, Solares FR,Tishler R, Stevenson R, Coleman N, Shafman T, Kaplan, I and Norregaard T, The Clinical State of Boron Neutron Capture Therapy Workshop, Department of Energy, Chasrlotte, NC; Nov. 3-5 (1997).
  • 7. Hawhorne MF, Angew Chem Int Ed Engl 32:950 (1993).
  • 8. Chen SY, Burnham BS, Spielvogel BF, Sood A, Wyrich SD and Hall IH, Appl Organomet Chem 10:279 (1998).
  • 9. Soloway AH, Tjark W, Barnum BA, Rong F-G, Barth RF, Codogni IM and Wilson JG, Chem Rev (ACS) 98:1515 (1998).
  • 10. Davidson MG, Hughes AK, Marder TB and Wade K (Eds.), Contemporary Boron Chemistry, The Royal Society of Chemistry, Cambridge (2000).
  • 11. Martin-Jimenez JL, Carretero-Colon JM, Martinez-Sanz A and Krause W, ES Pat. 9400034 (1995).
  • 12. Yang W, Gao X and Wang B, Med Res Rev 23:346 (2003).
  • 13. Kne RR and Hawthorne MF, US Pat. 9403272 (1995).
  • 14. Sarhan A and Wulff G, Makromol Chem 183:85 (1982).
  • 15. Uzundoğan E, Kayı H, Denkbaş EB, Patır S and Tuncel A, Polym Int 52:649 (2003).
  • 16. Zenk R and Partzch S, Chem Orggi 70:70 (2003).
  • 17. Advances in Boron Chemistry, ed by SiebertW, The Royal Society of Chemistry, Cambrige, UK (1987).
  • 18. Cancer Neutron Capture Therapy, ed by Mishima Y, Plenum Press, New York (1996).
  • 19. Ichihashi M, Nakanishi T and Mishima Y, J Invest Dermatol 78:215 (1982).
  • 20. Schwyzer R, Do KQ,Eberle AN and Fauchere L, Helv Chim Acta 64:2078 (1981).
  • 21. Yang Q, Cheng G, Parab K, Sundararaman A and Jakle F, Macromol Symp196:337 (2003).
  • 22. De Vos DE, Vankelecom IFJ and Jacobs, PA, Chiral Catalyst Immobilization and Recycling, Wiley-VCH, New York (2000).
  • 23. Sherrington DC and Kybetti AC, Supported Catalysts and Their Applications, The Royal Society of Chemistry, Cambridge (2001).
  • 24. Appleton B and Gibson TD, Sensors and Actuators 65B:302 (2000).
  • 25. Nicolas M, Fabre B and Simonet J. J Electroanal Chem 509:73 (2001).
  • 26. Boffa LS and Novak BM, Chem Rev 100:1479 (2000).
  • 27. Kondo Y, Garcia-Cuadrado D, Hartwig JF, Boaen NK, Wagner NL and Hillmyer MA, J Am Chem Soc 124:1164 (2002).
  • 28. Metha MA, Fujinami T and Inıue T, J Power Sources 81-82:724 (1999).
  • 29. Matsumi N, Sugai K and Ohno H, Macromolecules 35:5731 (2001).
  • 30. Sun X and Angell CA, Electrochimica Acta 46:1467 (2001).
  • 31. Armitage, P, Ebdon JR, Hunt BJ, Jones MS and Thorpe FG, Polym Degrad Stab 54:387 (1996).
  • 32. Gao J, Liu Y and Wang F, Eur Polym J 37:207 (2001).
  • 33. Seyferth D, Adv Chem Ser 245:131 (1995).
  • 34. Riedel R, Kroke E, Greiner A, Gabriel AO, Ruwisch L, Nicolich J and Kroll P, Chem Mater 10:2964 (1998)..
  • 35. Weinmann M, KamphoweTW, Schulmacher J, Müller K and Aldinger F, Chem Mater 2:2112 (2000).
  • 36. Kho J-G, Moon K-T, Nouet G, Ruterana P and Kim D-P, Thin Solid Films 389:78 (2001).
  • 37. Matsumi N, Naka K and Chujo Y, J Am Chem Soc 120:3112 (1998).
  • 38. Brunner AR, Bujalski DR, Moyer ES,Su K and Aldinger F, Chem Mater 12:2770 (2000).
  • 39. Valliant JF,Guenther AS,King P, Morel P, Schaffer OO and Sogbein KAS, Coordination Chem Rev 232:173 (2000).
  • 40. Parrott MC, Marchington EB, Valliani JF and Adronov A, Macromol Symp 196:201 (2003).
  • 41. Kahraman G, Beşkardeş O, Rzaev ZMO and Pişkin E, Polymer 44:2897 (2003).
  • 42. Rzaev ZMO, Kircı B, Çimen EK and Pişkin E, 40th IUPAC World Polymer Congress, Paris, France, 2004, Congress Proc. # 959.
  • 43. Çimen, EK, Rzaev ZMO and Pişkin E, J Appl Polym Sci 95:573 (2005).
  • 44. Dinçer S, Kesim H, Rzaev ZMO and Pişkin E, Eur Polym J 38:43 (2002).
  • 45. Köseli V, Rzaev ZMO and Pişkin E, J Polym Sci Part A: Polym Chem 41:1580 (2003).
  • 46. Türk M, Dinçer S, Yuluğ IG and Pişkin E, J Control Rel 96:325 (2004).
  • 47. Sugai S, Nitta K, and Ohno N, Polymer 23:238 (1982).
  • 48. Ohno N and Sugai S, Macromolecules 18:1287 (1985).